Process for preparing aromatic olefins in the presence of palladium catalysts comprising phosphite ligands
First Claim
Patent Images
1. A process for preparing monofunctional, bifunctional or/and polyfunctional olefins of the formulae (Ia), (Ib), (Ic) or/and (Id), whereR1 to R3 are, independently of one another, hydrogen, (C1-C8)-alkyl, CN COOH, COO-alkyl-(C1-C8), aryl-(C6-C10), COO-aryl-(C6-C10), CO-aryl-(C6-C10), O-alkyl-(C1-C8), O—
- CO-alkyl-(C1-C8), N-alkyl2-(C1-C8) and aryl is an aromatic radical containing up to 14 carbon atoms, where this radical may bear up to five substituents which are, independently of one another, hydrogen, (C1-C8)-alkyl, O-alkyl-(C1-C8), OCO-alkyl-(C1-C8), O-phenyl, phenyl, aryl, fluorine, chlorine, OH, NO2, Si(alkyl-(C1-C8))3,CN, COOH, CHO, SO3H, NH2, NH-alkyl-(C1-C8), N-alkyl2-(C1-C8), P-alkyl2-(C1-C8), SO2-alkyl-(C1-C6), SO-alkyl-(C1-C6), CF3, NHCO-alkyl-(C1-C4), COO-alkyl-(C1-C8), CONH2, CO-alkyl-(C1-C8), NHCOH, NHCOO-alkyl-(C1-C4), CO-phenyl, COO-phenyl, CHCH—
CO2-alkyl-(C1-C8), P(phenyl)2, CHCHCO2H, PO-phenyl2, POalkyl2-(C1-C4), PO3H2, PO(O-alkyl-(C1-C6))2, SO3-alkyl-(C1-C4) where aryl is as defined above, and where R1a to R7a are, independently of one another, hydrogen, (C1-C8)-alkyl, O-alkyl-(C1-C8), OCO-alkyl-(C1-C8), O-phenyl, phenyl, aryl, fluorine, chlorine, OH, NO2, Si(alkyl-(C1-C8))3, CN, COOH, CHO, SO3H, NH2, NH-alkyl-(C1-C8), N-alkyl2-(C1-C8), P-alkyl2-(C1-C8), SO2-alkyl-(C1-C6)-alkyl-(C1-C6), CF3, NHCO-alkyl-(C1-C4), COO-alkyl-(C1-C8), CONH2, CO-alkyl-(C1-C8), NHCOH, NHCOO-alkyl-(C1-C4), CO-phenyl, COO-phenyl, CHCH—
CO2-alkyl-(C1-C8), P(phenyl)2, CHCHCO2H, PO-phenyl2, POalkyl2-(C1-C4), PO3H2, PO(O-alkyl-(C1-C6))2, SO3-alkyl-(C1-C4), where aryl is as defined above, and is a heteroaromatic, where the heteroaromatic Ar can be a substituted 5-, 6- or 7-membered ring containing, if desired, nitrogen, oxygen or sulfur atoms in the ring, where further aromatic, heteroaromatic and/or aliphatic rings can be fused onto the ring, and where the heteroaromatic can have substituents which are, independently of one another, hydrogen, (C1-C8)-alkyl, O-aryl, aryl, fluorine, chlorine, OH, NO2, CN, CO2H, CHO, SO3H, NH2, NH-alkyl-(C1-C12), N-alkyl2-(C1-C12), CHCHCO2H, NHCO-alkyl-(C1-C12), CO-alkyl-(C1-C12), NHCHO, COaryl, CO2aryl, CF3, CONH2, POaryl2, POalkyl2-(C1-C12), Si(alkyl-(C1-C2))3,O-alkyl-(C1-C8), OCO-alkyl-(C1-C8), O-phenyl, phenyl, NH-alkyl-(C1-C4), COO-alkyl-(C1-C8), NHCOO-alkyl-(C1-C4), CO-phenyl, COO-phenyl, CHCH—
CO2-alkyl-(C1-C8), PO-phenyl2, PO3H2, SO3-alkyl-(C1-C4), SO2-alkyl-(C1-C4), SO-alkyl-(C1-C4), where aryl is as defined above, and where R8a to R10a are, independently of one another, hydrogen, CN, CO2H, CO2-alkyl-(C1-C8), CONH2, CONH-alkyl-(C1-C4), CON-(alkyl)2-(C1-C4), fluorine, CO2-phenyl, alkyl-(C1-C8)yl, phenyl, aryl, PO(phenyl)2, PO[alkyl-(C1-C4)]2, CO-phenyl, CO-alkyl-(C1-C4), O-alkyl-(C1-C4), CONH-alkyl-(C1-C8), CONH-alkyl-(C1-C8)2,NH-alkyl-(C1-C4), PO3H2, SO3H, SO3-alkyl-(C1-C4), SO2-alkyl-(C1-C4), O-phenyl, where aryl is as defined above, by reacting haloaromatics, haloolefins or/and heterohaloaromatics of the formulae (IIa), (IIb), (IIc) or/and (IId)with olefins of the fornula (III),
where, in the formulae of the type II and III, R1 to R3 and R1a to R10a are as defined above for the formulae of the type (I) and where X is iodine, bromine, chlorine, OSO2CF3, OSO2-phenyl, OSO2-tolyl, OSO2-alkyl-(C1-C8), wherein a mixture of a palladium(0) complex or a palladium(II) salt with phosphite ligands of the formulae (IVa) or/and (IVb),
the formula (IVb) represents a chelating phosphite ligand and where the radicals R11a to R14a are identical or different and are each, independently of one another, (C1-C18)-alkyl or/and a substituted (C1-C18)-alkyl group having the substituents hydrogen, O-alkyl-(C1-C8), O—
CO-alkyl-(C1-C8), O-phenyl, phenyl, fluorine, chlorine, OH, NO2, CN, COOH, CHO, SO3H, SO2-alkyl-(C1-C8), SO-alkyl-(C1-C8), NH2, NH-alkyl-(C1-C8), N-alkyl2-(C1-C8), NHCO-alkyl-(C1-C4), CF3, COO-alkyl-(C1-C8), CONH2, CO-alkyl-(C1-C8), NHCOH, NHCOO-alkyl-(C1-C4), CO-phenyl, COO-phenyl, CHCH—
CO2-alkyl-(C1-C8), CHCHCO2H, PO-phenyl2, POalkyl2-(C1-C8), or the radicals R11a to R14 are an aromatic Ar′
, where Ar′
is a substituted phenyl, naphthyl, anthryl, phenanthryl or biphenyl radical or/and a 5-, 6- or 7-membered heteroaromatic containing, optionally nitrogen, oxygen or sulfur atoms in the ring, where the aromatics may contain up to ten substituents which are (C1-C8)-alkyl, OAr′
, Ar′
, fluorine, chlorine, OH, NO2, CN, CO2H, CHO, SO3H, NH2, NH-alkyl-(C1-C12), N-alkyl2-(C1-C12), NHCO-alkyl-(C1-C12), CO-alkyl-(C1-C12), NHCHO, COAr′
, CO2Ar′
, CF3, CONH2, CHCHCO2H, POAr′
s, POalkyl2-(C1-C12), Si(alkyl-(C1-C12))3,O-alkyl-(C1-C8), OCO-alkyl-(C1-C8), O-phenyl, phenyl, COO-alkyl-(C1-C8), NHCOO-alkyl-(C1-C4), CO-phenyl, COO-phenyl, CHCH—
CO2-alkyl-(C1-C8), PO-phenyl2, PO3H2, SO3-alkyl-(C1-C4), SO2-alkyl-(C1-C4), SO-alkyl-(C1-C8), where the carbon bridge of the phosphite ligand C2 to C4 may have up to four substituents which are identical or different and are, hydrogen, (C1-C4)-alkyl, O-alkyl-(C1-C4), OH, aryl or/and phenyl, where aryl is as defined above.
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Abstract
The invention relates to process for preparing monofunctional, bifunctional or/and polyfunctional olefins of the formulae (Ia), (Ib), (Ic) or/and (Id),
where R1 to R3 are, independently of one another, hydrogen, (C1-C8)-alkyl, CN, COOH, COO-alkyl-(C1-C8), CO-alkyl-(C1-C8), aryl-(C6-C10), COO-aryl-(C6-C10), CO-aryl-(C6-C10), O-alkyl-(C1-C8), O—CO-alkyl-(C1-C8) or N-alkyl2-(C1-C8) and aryl is an aromatic radical containing up to 14 carbon atoms, where aryl is as defined above, and Ar is a heteroaromatic,
by reacting haloaromatics, haloolefins or/and heterohaloaromatics of the formulae (IIa), (IIb), (IIc) or/and (IId) with olefins of the formula (III),
wherein a mixture of a palladium(0) complex or a palladium(II) salt with phosphite ligands of the formulae (IVa) or/and (IVb)
is used as catalyst.
5 Citations
19 Claims
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1. A process for preparing monofunctional, bifunctional or/and polyfunctional olefins of the formulae (Ia), (Ib), (Ic) or/and (Id),
where R1 to R3 are, independently of one another, hydrogen, (C1-C8)-alkyl, CN COOH, COO-alkyl-(C1-C8), aryl-(C6-C10), COO-aryl-(C6-C10), CO-aryl-(C6-C10), O-alkyl-(C1-C8), O— - CO-alkyl-(C1-C8), N-alkyl2-(C1-C8) and aryl is an aromatic radical containing up to 14 carbon atoms, where this radical may bear up to five substituents which are, independently of one another, hydrogen, (C1-C8)-alkyl, O-alkyl-(C1-C8), OCO-alkyl-(C1-C8), O-phenyl, phenyl, aryl, fluorine, chlorine, OH, NO2, Si(alkyl-(C1-C8))3,CN, COOH, CHO, SO3H, NH2, NH-alkyl-(C1-C8), N-alkyl2-(C1-C8), P-alkyl2-(C1-C8), SO2-alkyl-(C1-C6), SO-alkyl-(C1-C6), CF3, NHCO-alkyl-(C1-C4), COO-alkyl-(C1-C8), CONH2, CO-alkyl-(C1-C8), NHCOH, NHCOO-alkyl-(C1-C4), CO-phenyl, COO-phenyl, CHCH—
CO2-alkyl-(C1-C8), P(phenyl)2, CHCHCO2H, PO-phenyl2, POalkyl2-(C1-C4), PO3H2, PO(O-alkyl-(C1-C6))2, SO3-alkyl-(C1-C4) where aryl is as defined above, and whereR1a to R7a are, independently of one another, hydrogen, (C1-C8)-alkyl, O-alkyl-(C1-C8), OCO-alkyl-(C1-C8), O-phenyl, phenyl, aryl, fluorine, chlorine, OH, NO2, Si(alkyl-(C1-C8))3, CN, COOH, CHO, SO3H, NH2, NH-alkyl-(C1-C8), N-alkyl2-(C1-C8), P-alkyl2-(C1-C8), SO2-alkyl-(C1-C6)-alkyl-(C1-C6), CF3, NHCO-alkyl-(C1-C4), COO-alkyl-(C1-C8), CONH2, CO-alkyl-(C1-C8), NHCOH, NHCOO-alkyl-(C1-C4), CO-phenyl, COO-phenyl, CHCH—
CO2-alkyl-(C1-C8), P(phenyl)2, CHCHCO2H, PO-phenyl2, POalkyl2-(C1-C4), PO3H2, PO(O-alkyl-(C1-C6))2, SO3-alkyl-(C1-C4), where aryl is as defined above, and is a heteroaromatic, where the heteroaromatic Ar can be a substituted 5-, 6- or 7-membered ring containing, if desired, nitrogen, oxygen or sulfur atoms in the ring, where further aromatic, heteroaromatic and/or aliphatic rings can be fused onto the ring, and where the heteroaromatic can have substituents which are, independently of one another, hydrogen, (C1-C8)-alkyl, O-aryl, aryl, fluorine, chlorine, OH, NO2, CN, CO2H, CHO, SO3H, NH2, NH-alkyl-(C1-C12), N-alkyl2-(C1-C12), CHCHCO2H, NHCO-alkyl-(C1-C12), CO-alkyl-(C1-C12), NHCHO, COaryl, CO2aryl, CF3, CONH2, POaryl2, POalkyl2-(C1-C12), Si(alkyl-(C1-C2))3,O-alkyl-(C1-C8), OCO-alkyl-(C1-C8), O-phenyl, phenyl, NH-alkyl-(C1-C4), COO-alkyl-(C1-C8), NHCOO-alkyl-(C1-C4), CO-phenyl, COO-phenyl, CHCH—
CO2-alkyl-(C1-C8), PO-phenyl2, PO3H2, SO3-alkyl-(C1-C4), SO2-alkyl-(C1-C4), SO-alkyl-(C1-C4), where aryl is as defined above, and whereR8a to R10a are, independently of one another, hydrogen, CN, CO2H, CO2-alkyl-(C1-C8), CONH2, CONH-alkyl-(C1-C4), CON-(alkyl)2-(C1-C4), fluorine, CO2-phenyl, alkyl-(C1-C8)yl, phenyl, aryl, PO(phenyl)2, PO[alkyl-(C1-C4)]2, CO-phenyl, CO-alkyl-(C1-C4), O-alkyl-(C1-C4), CONH-alkyl-(C1-C8), CONH-alkyl-(C1-C8)2,NH-alkyl-(C1-C4), PO3H2, SO3H, SO3-alkyl-(C1-C4), SO2-alkyl-(C1-C4), O-phenyl, where aryl is as defined above, by reacting haloaromatics, haloolefins or/and heterohaloaromatics of the formulae (IIa), (IIb), (IIc) or/and (IId) with olefins of the fornula (III), where, in the formulae of the type II and III, R1 to R3 and R1a to R10a are as defined above for the formulae of the type (I) and where X is iodine, bromine, chlorine, OSO2CF3, OSO2-phenyl, OSO2-tolyl, OSO2-alkyl-(C1-C8), wherein a mixture of a palladium(0) complex or a palladium(II) salt with phosphite ligands of the formulae (IVa) or/and (IVb), the formula (IVb) represents a chelating phosphite ligand and where the radicals R11a to R14a are identical or different and are each, independently of one another, (C1-C18)-alkyl or/and a substituted (C1-C18)-alkyl group having the substituents hydrogen, O-alkyl-(C1-C8), O—
CO-alkyl-(C1-C8), O-phenyl, phenyl, fluorine, chlorine, OH, NO2, CN, COOH, CHO, SO3H, SO2-alkyl-(C1-C8), SO-alkyl-(C1-C8), NH2, NH-alkyl-(C1-C8), N-alkyl2-(C1-C8), NHCO-alkyl-(C1-C4), CF3, COO-alkyl-(C1-C8), CONH2, CO-alkyl-(C1-C8), NHCOH, NHCOO-alkyl-(C1-C4), CO-phenyl, COO-phenyl, CHCH—
CO2-alkyl-(C1-C8), CHCHCO2H, PO-phenyl2, POalkyl2-(C1-C8),or the radicals R11a to R14 are an aromatic Ar′
, where Ar′
is a substituted phenyl, naphthyl, anthryl, phenanthryl or biphenyl radical or/and a 5-, 6- or 7-membered heteroaromatic containing, optionally nitrogen, oxygen or sulfur atoms in the ring,where the aromatics may contain up to ten substituents which are (C1-C8)-alkyl, OAr′
, Ar′
, fluorine, chlorine, OH, NO2, CN, CO2H, CHO, SO3H, NH2, NH-alkyl-(C1-C12), N-alkyl2-(C1-C12), NHCO-alkyl-(C1-C12), CO-alkyl-(C1-C12), NHCHO, COAr′
, CO2Ar′
, CF3, CONH2, CHCHCO2H, POAr′
s, POalkyl2-(C1-C12), Si(alkyl-(C1-C12))3,O-alkyl-(C1-C8), OCO-alkyl-(C1-C8), O-phenyl, phenyl, COO-alkyl-(C1-C8), NHCOO-alkyl-(C1-C4), CO-phenyl, COO-phenyl, CHCH—
CO2-alkyl-(C1-C8), PO-phenyl2, PO3H2, SO3-alkyl-(C1-C4), SO2-alkyl-(C1-C4), SO-alkyl-(C1-C8), where the carbon bridge of the phosphite ligand C2 to C4 may have up to four substituents which are identical or different and are, hydrogen, (C1-C4)-alkyl, O-alkyl-(C1-C4), OH, aryl or/and phenyl, where aryl is as defined above.- View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19)
Si(alkyl-(C1-C12))3,O-alkyl-(C1-C8), OCO-alkyl-(C1-C8), O-phenyl, phenyl, COO-alkyl-(C1-C8), NHCOO-alkyl-(C1-C4), CO-phenyl, COO-phenyl, CHCH— - CO2-alkyl-(C1-C8), PO-phenyl2, PO3H2, SO3-alkyl-(C1-C4), SO2-alkyl-(C1-C4), SO-alkyl-(C1-C4), where aryl is as defined above, and R8a to R10a are identical or different and are, independently of one another, hydrogen, CN, CO2H, phenyl, CO2alkyl-(C1-C8), CONH2, F, O-alkyl-(C1-C4), alkyl-(C1-C8), NH-alkyl-(C1-C4).
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3. The process as claimed in claim 1, wherein the olefins prepared are ones of the formula (Ia) in which R1 to R3 is hydrogen, (C1-C4)-alkyl or/and phenyl.
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4. The process for preparing compounds of the formulae (Ia), (Ib), (Ic) or/and (Id) as claimed in claim 1, wherein R1 to R3 and R1a to R7a are, independently of one another, hydrogen, (C1-C8)-alkyl, O-alkyl-(C1-C8), O—
- CO-alkyl-(C1-C8), N-alkyl2-(C1-C8), phenyl, aryl, fluorine, chlorine, NO2, CN, COOH, CHO, SO2-alkyl-(C1-C4),NH-(C1-C8)-alkyl, N[(C1-C8)-alkyl]2, COO-(C1-C8)-alkyl, CONH2, CO-(C1-C8)-alkyl, CO-phenyl or/and PO(phenyl)2, where aryl is as defined above, and R8a to R10a are, independently of one another, hydrogen, CN, CO2H, CO2-alkyl-(C1-C8), CONH2, F, O-alkyl-(C1-C4), alkyl-(C1-C8), NH-alkyl-(C1-C4), CONH-alkyl-(C1-C8), CON[alkyl-(C1-C8)]2, phenyl or/and aryl, where aryl is as defined above.
-
5. The process as claimed in claim 1, where said solvent is an inert organic solvent, water or mixture thereof.
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6. The process as claimed in claim 1, wherein the reaction proceeds at temperatures of from 20 to 200°
- C. with the pressure being able to be up to 100 bar.
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7. The process as claimed in claim 1, wherein HX which is eliminated in the reaction is neutralized by addition of a base.
-
8. The process as claimed in claim 1, wherein the palladium catalysts (IV) used are generated in situ from palladium(II) salts and the corresponding phosphite ligands.
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9. The process as claimed in claim 1, wherein the palladium catalysts (IV) used are used directly as palladium(0) phosphite complexes.
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10. The process as claimed in claim 1, wherein palladium-containing precursors used are palladium(II) acetate, palladium(II) chloride, palladium(II) bromide, lithium tetrachloropalladate, palladium(II) acetylacetonate, palladium(0)-dibenzylidene-acetone complexes, tetrakisylitylriphenylphosphine)palladium(0), bis(tri-O-tolyl-phosphine)palladium(0), palladium(II) propionate, bis(acetonitrile)palladium(II) chloride, bis(triphenylphosphine)palladium(II) dichlorideyl, palladium(0)-tricyclohexylphosphine-(diallyl ether) complex, bis(tricyclohexylphosphine)-palladium(0), bis(benzonitrile)palladium(II) chloride or/and further palladium(0) and palladium(II) complexes.
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11. The process as claimed in claim 1, wherein use is made of a chelating phosphite ligand whose carbon bridge C2 to C4 has up to four identical or different substituents.
-
12. The process as claimed in claim 1, wherein the catalyst is used in a palladium:
- ligand ratio of from 1;
2 to 1;
200.
- ligand ratio of from 1;
-
13. The process as claimed in claim 1, wherein a cocatalyst, is added to the palladium phosphite catalyst.
-
14. The process as claimed in claim 1, wherein the cocatalyst is added in an amount of from 0.01 mol % to 50 mol %.
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15. The process as claimed in claim 1, wherein the reaction is carried out in the cocatalyst as solvent.
-
16. The process as claimed in claim 1, wherein catalyst contents of ≦
- 2 mol%, are used.
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17. The process as claimed in claim 2, wherein the heterohaloaromatics ArX of the formula (IId) which are used are substituted heterohaloaromatics having up to four heteroatoms and the heteroatoms are N, O, or S or a mixture thereof.
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18. The process as claimed in claim 2, wherein the heterohaloaromatics ArX of the formula (IId) are pyridines, pyrimidines, oxazoles, imidazoles, pyrazines, quinolines, indoles, furans, benzofurans or/and thiophenes.
-
19. The process as claimed in claim 14, wherein the catalyst is used in a palladium:
- ligand ratio of from 1;
5 to 1;
200 and the cocatalyst is added in an amount of from 0.1 to 50 mol %.
- ligand ratio of from 1;
- CO-alkyl-(C1-C8), N-alkyl2-(C1-C8) and aryl is an aromatic radical containing up to 14 carbon atoms, where this radical may bear up to five substituents which are, independently of one another, hydrogen, (C1-C8)-alkyl, O-alkyl-(C1-C8), OCO-alkyl-(C1-C8), O-phenyl, phenyl, aryl, fluorine, chlorine, OH, NO2, Si(alkyl-(C1-C8))3,CN, COOH, CHO, SO3H, NH2, NH-alkyl-(C1-C8), N-alkyl2-(C1-C8), P-alkyl2-(C1-C8), SO2-alkyl-(C1-C6), SO-alkyl-(C1-C6), CF3, NHCO-alkyl-(C1-C4), COO-alkyl-(C1-C8), CONH2, CO-alkyl-(C1-C8), NHCOH, NHCOO-alkyl-(C1-C4), CO-phenyl, COO-phenyl, CHCH—
Specification
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Current AssigneeDegussa AG (Rag-Stiftung)
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Original AssigneeAventis Research & Technologies GmbH & Co. KG (Bristol-Myers Squibb Company)
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InventorsRiermeier, Thomas, Beller, Matthias, Zapf, Alexander
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Primary Examiner(s)Shah, Mukund J.
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Assistant Examiner(s)Patel, Sudhaker B.
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Application NumberUS09/326,404Time in Patent Office837 DaysField of Search502/103US Class Current502/103CPC Class CodesC07B 37/04 SubstitutionC07C 17/266 of hydrocarbons and halogen...C07C 2/861 the non-hydrocarbon contain...C07C 201/12 by reactions not involving ...C07C 205/56 having nitro groups bound t...C07C 22/08 containing fluorineC07C 231/12 by reactions not involving ...C07C 233/11 with carbon atoms of carbox...C07C 2531/02 containing organic compound...C07C 2531/22 Organic complexesC07C 41/30 by increasing the number of...C07C 43/215 having unsaturation outside...C07C 45/68 by increase in the number o...C07C 49/796 polycyclic
